Cumulenylidene synthesis

Another example for the Tp versus bdmpza analogy is the synthesis of various bdmpza ruthenium cumulenylidene complexes. The... 

Abstract Allenylidene complexes have gained considerable significance in the context of transition-metal carbene chemistry due to their potential applications in organic synthesis. The aim of this chapter is to draw together a general presentation of the most efficient synthetic routes, the main structural features and reactivity patterns, as well as current applications in homogeneous catalysis, of aU-carbon-substituted allenylidenes and related cumulenylidene complexes containing an odd number of carbon atoms. 

The metal-ligand fragment L M, the number of carbon atoms x, and the substituents at the terminal sp -carbon may vary considerably and, correspondingly, the properties and reactivities. The early members of the series of cumulenylidene complexes (x=l, 2, 3 carbene, vinylidene and allenylidene complexes) have established themselves as invaluable building blocks in stoichiometric synthesis and as highly potent catalyst precursors. The higher members might potentially be very useful candidates for application as one-dimensional wires and in opto-electronic devices. 

Metal allenylidene complexes (M=C=C=CR2) are organometallic species having a double bond betv een a metal and a carbon, such as metal carbenes (M=CR2), metal vinylidenes (M=C=CR2), and other metal cumulenylidenes like M=C=C= C=CR2 [1]. These metal-carbon double bonds are reactive enough to be employed for many organic transformations, both catalytically and stoichiometrically [1, 2]. Especially, the metathesis of alkenes via metal carbenes may be one ofthe most useful reactions in the field of recent organic synthesis [3], vhile metal vinylidenes are also revealed to be the important species in many organic syntheses such as alkyne polymerization and cycloaromatization [4, 5]. 

Cumulenylidenes, LhM=C=C=CR1, L M=C=C=C=C=CR, This should include an appreciation of suitable synthetic strategies, typical reactions and selected applications to organic synthesis (stoichiometric and catalytic). 

Also, bi- and trimetallic cumulene complexes, such as M=C=M, M=M=C, M=M=M and M=C=C=M are known. Cationic ruthenium allenylidene complexes are used as catalysts for ring closing metathesis reactions. Nonlinear optical properties have been measured for the Group 6 cumulenylidene complexes. Also, cationic chromium or iron vinylidene complexes undergo [2-1-2] cycloaddition reactions across imines to give fi-lactams. This reaction is useful for the synthesis of j8-lactam antibiotics. ... 

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